Aromaticity is a central concept in chemistry. Reaction pathways involving reversible ligand dearomatization sequences emerged as a powerful tool for bond activation by metal complexes. Exploring this concept with a metal-free system, we have synthesized a pyridine-coordinated amino-borane which undergoes a temperature-induced formal dearomatization of the pyridine ring. NMR studies and DFT calculations revealed that this formal dearomatization sequence led to an aromaticity switch and the formation of a six-pi-electron boron-containing heteroaromatic system. Disrupting this aromatic system by coordination of an amine or a carboxylic acid to the boron center enabled N-H activation and O-H cleavage, leading to an unprecedented reversal aromaticity switch.